Selective E to Z isomerization of 1,3-Dienes Enabled by A Dinuclear Mechanism

• Published in: Nature communications Vol. 12; no. 1; p. 1473
• Main Authors: Kudo, Eiji, Sasaki, Kota, Kawamata, Shiori, Yamamoto, Koji, Murahashi, Tetsuro
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 05.03.2021; Nature Publishing Group; Nature Portfolio
• Subjects: 119/118; 140/131; 140/58; 639/638/263/406/910; 639/638/403/935; 639/638/549/933; Carbon; Chemical energy; Dienes; Energy; Equilibrium; Humanities and Social Sciences; Injection; Isomerization; Isomers; multidisciplinary; Science; Science (multidisciplinary); Trapping
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-021-21720-4

The E / Z stereocontrol in a C=C bond is a fundamental issue in olefin synthesis. Although the thermodynamically more stable E geometry is readily addressable by thermal Z to E geometric isomerization through equilibrium, it has remained difficult to undergo thermal geometric isomerization to the reverse E to Z direction in a selective manner, because it requires kinetic trapping of Z -isomer with injection of chemical energy. Here we report that a dinuclear Pd I −Pd I complex mediates selective isomerization of E -1,3-diene to its Z -isomer without photoirradiation, where kinetic trapping is achieved through rational sequences of dinuclear elementary steps. The chemical energy required for the E to Z isomerization can be injected from an organic conjugate reaction through sharing of common Pd species. Geometric E to Z double C=C bond isomerization is challenging as it requires kinetic trapping of the Z -isomer with injection of chemical energy. Here, the authors report a dinuclear Pd(I)−Pd(I) complex that mediates selective isomerization of E -1,3-dienes to the Z -isomers without photoirradiation.